Azo anthraquinone vat dyes and intermediates



particular dyes available.

Patented July 10, 195i AZO AN THRAQUINONE VAT DYES AND IN TERMEDIATES Herman E. Schroeder, Wilmington, Del., and Joseph Deinet, Glassboro, N. J., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware N Drawing. Application June 17, 1949, Serial No. 99,872

6 Claims. (Cl. 260-157) This invention relates to anthraquinone vat dyes and intermediates, and more particularly to monoanthraquinone oxazoles and thiazoles of azobiphenyldicarboxylic acid.

It has been recognizedfor many years that, in thedyes of the anthraquinone series, those in the yellow range are generally deficient in their fastness properties, more particularly with regard to fastness to light, although in general the dyes of the anthraquinone vat dye class are considered to have good fastness properties. Where yellow dyes have been found in the anthraquinone series which have good fastness properties, they are usually either dull or weak tinctorially, and therefore the various dyes in the anthraquinone vat dye class must be selected to answer the particular need at hand, balancing the question of fastness, brightness and tinctorial strength of the In U. S. Patent 2,175,803 a group of symmetrical dianthraquinonediazoles, more particularly imidazoles, 1,2 (N) thiazoles and 2,1(N) oxazoles which contain an azo group, are disclosed. These compounds dye vegetable fibers in yellowish shades and are said to exhibit good fastness to chlorine and boiling soap solution, and, in many cases, to light. It has been found, however, that these dyes are deficient in wet fastness, particularly in kier boiling, and in their vat stability. In U. S. Patent 2,228,455 a series of dianthraquinonylimides containing'azo groups are disclosed which have relatively good fastness properties, but these dyes have been found to be dull and considerably weaker than theazole types of the first mentioned patent.

It is an object of this invention to prepare new anthraquinone oxazoles and thiazoles of azobiphenyldicarboxylic acid which are valuable as dyes, pigments and intermediates for the preparation of other dyes. It is a further object of the invention to prepare new and valuable yellow dyes of the anthraquinone series which dye cellulose fibers from the usual alkaline hydrosulfite vats in strong shades which have outstanding fastness properties.

We have found that, where the azobiphenylcarbonylaminoanthraquinone compounds of the formula:

in'which X stands for a substituent of the group consisting of Cl, Br and SH, y stands for an element of the group consisting of H, Cl and Br and R stands for' a radical of the group consist- 2 ing of OI-I, --Cl, O-alkyl, -NH2, NH-alkyl, and NH-aryl in which the O-alkyl group may; carry from 1 to 18 carbon atoms, the NI-I-alkyl group from 1 to 4 carbon atoms and the aryl group is a hydrocarbon radical of the benzene and naphthalene series, are ring closed to form the oxazole or thiazole ring, new compounds are obtained which are of value as dyes, pigments and intermediates for other dyes, which have the formula:

in which X stands for an element of the group: consisting of O and S and y and R have the same significance as given above.

These simple carboxylic acid compounds possess exceptional and unexpected merit as light-fast pigments and vat dyes. Very surprisingly, only a single anthraquinone nucleus is-suificient toconfer vattability on a group of productswith molecular weights over 500. I

The compounds of this invention are formed by the condensation of equal molecular ratios of 4,4 azobiphenyl-4 Q4 dicarbonyl chloride with a 1halogen-2aminoanthraquinone with further conversion of the remaining free acid chloride group to the free acid, the acid amide, the alkyl ether or the arylor alkyl-amide derivative where such compounds are to be produced, followed by ring closure tothe oxazole. A number of the intermediates useful for producing compounds of the present invention are disclosed and. claimed in our co-pending application Serial No. 99,871.

Alternatively, 1mercapto-Zaminoanthraquinone can be used instead of the halogen derivative, thus giving rise to a thiazole instead of an; oxazole. Bright, strong yellow products are! formed. They are filtered off, purified if desired by known means such as by acid pasting or alkaline hypochlorite bleaching, and converted into pastes or powders for various applications as. dyes or pigments. If desired, certain of the oxazole products, and particularly the free car-- boxylic acid, can be converted to the acid halide and subjected to condensation with vattable amines to give further, dyes of the type disclosed'l in co-pending applications Serial Nos. 99,873, 99,-f 877, 99,878 and 99,880. The following examples are given to illustrate the invention. The parts-used are by-weight, unless otherwise specified. 1

, E l' 1 sixty parts of 4,4-azobiphenyl-4QT -di mass is heated to 135-l38 C. and maintained for 6 hours. It is cooled to 120 C., 25 parts of water are added (slowly) and the mass is heated to l25-130 C. and maintained for 6 hours. Itis cooled to 100 C., 50 parts of sodium carbonate, "50

parts of potassium acetate, 1.5 parts oi cupric V acetate and 1.5 parts oi cuprous chloride are added; the mass is heated, to 210 C., and maintained for 6 hours. After cooling, the mass is filtered, the cake washed with nitrobenzene, alcohol and hot water in turn, and dried. It is obtained in good yields and has the following formula:

It is a yellow solid, gives a red-brown sodium hydrosulfite vat (violet cast) and dyes and prints cotton in bright yellow shades of very good tastness properties.

Example 2 It is a yellow solid and it is easily decomposed by concentrated sulfuric acid to the free acid (COOH) Example 3 Forty (40) parts of 1-chloro2-aminoanthraquinone, 77 parts of 4,4'-azobiphenyl-4",4-dicarboxylic acid chloride and 1500 parts of nitrobenzene and 0.5 part of pyridine are heated together to 140 C. and maintained, for 6 hours. It is then cooled to'125" C. and treated with ammonia (by leading a weak stream of NH: into the reaction mass) for 3 to 4 hours. Then 50 parts of sodium carbonate, 50'parts of, potassium acetate, 1.5 parts of cupricf'acet'ate and 1.5 parts of cuprous chloride are added, the massis heated to 210 C. and maintained for 6 hours. After cooling the mass is filtered, the cake washed with alcohol and hot .water, in turn, and dried. It is 4 obtained in good yields and has the following formula:

It is a yellow solid, gives a red-brown sodium hydrosulfite vat (violet cast) and dyes cotton in bright yellow shades of very good fastness properties.

Example 4 Thirty-three (33') parts of 1-chloro-2-aminoanthraquinone, 60 parts of 4,4-azobiphenyl-'4, 4"'-dicarboxylic acid chloride, 0.5 part of pyridine and 1200 parts of nitrobenzene are heated together to 138140 C. and maintained for 6 hours. Then 25. parts of methyl alcohol are slowly added at -135 C. and maintained for 3 hours. Then 50 parts of sodium carbonate, 50 parts of potassium acetate, 1.5 parts cupric acetate and 1.5 parts of cuprous chloride are added, the mass is heated to 210 C. and maintained for 6 hours. After cooling the mass is filtered, washed with alcohol and water, in turn, and dried. The product obtained has the following formula:

fl) O O0-BENUOC O O OH;

o It is a yellow solid, gives a red-brown sodium hydrosulfite vat (violet cast) and dyes and prints 7 in bright yellow shades of good fastness properties.

By replacing the methyl alcohol with 25 parts of dodecyl alcohol, a product of the following formula is obtained:

atoms are substituted for the methyl alcohol, such as the ethyl, isopropyl, butyl, octyl, cetyl and octadecyl, or other primary or secondary alcohols containing up to 18 carbon atoms, compounds are obtained which dye cellulose fibers from the usual alkaline hydrosulfite vats in bright yellow shades.

Example 5 added. The mass is heated to-138 C. and

maintained for 6 hours, then heated to 1'48 C. and maintained for 6 hours. It is cooled to 50 C., filtered, washed with benzene and dried.

2,5'59,66 it is obtained in very good yields and has the It is a yellow solid, gives a dull violet'sodium following formula: hydrosulfite vat (red-brown) and dyes and prints 0 COO1 cotton in bright yellow shades of very good fastness properties. N Example 7 A mixture of 1200 parts of nitrobenzene, 0.2 g part of pyridine, 100 parts of the following acid Upon treatment with concentrated sulfuric 10 c de! -NHO 0- N=N -o 0 0] acid, the free acid compound of the following (obtained by condensing 1-chloro-2-aminoanformula is obtained. thraquinone with 4,4-azobiphenyl-4.,4"'-d1- carboxylic acid chloride mol per mol) and 14 v COOH parts of aniline was heated together to 210 C. n and maintained for one hour. It 1s cooled to 100 0., when 50 parts of sodium carbonate, 50 parts of potassium acetate, 1.5 parts of cupric acetate and 1.5 parts of cuprous chloride were v added; then the reaction mass was heated to 210 C. and maintained for 6 hours. After cooling, the mass was filtered, the cake was washed It dyes and prints cotton from a dull violet With alcohol a d h Water in t and rie sodium hydrosulfite vat in bright yellow shades It is obtained in good yield and has the followof very good strength and fastness properties. ing formula:

Example 6 1 It is a yellow solid and dyes cotton in bright llow shades of very good fastness properties Sixty (60) parts of 4,4 -azob1phenyl-4' ,4 ye dicarboxylic acid (sodium salt) are suspended in g gggfig ggg gfi ififfi ig g amines Such 1200 parts of nitrobenzene, 1.5 parts of pyridine as methyl eth 1 iso r0 1 g but lammes and and parts of thionyl chloride are added while alpha gj i g g be used in agitating, 312d t1}; rlrliass is lliieatectlihto 95 and 50 condensation with the acid chlorides In place main aine or ours. is en air lown for one-half hour to take out excess of thionyl g: fi igggg i z 33 2 5 ifi g igfig figgg igggj chloride, and cooled to 50 0., when parts of thalene chloronaphthalene diphenyl ig 52 1 5 2 ig figf fig i igf ether, etc., can be used as solvents. Phosphorus tained for l2 hours. It is cooled to 120 C. 25 55 i be employed as chloride forming agent instead of thionyl chloride while parts of water are added (slowly) and the mass s as ring 61 05mg agents sodium or potassim'n car heated to 120-125 C. and maintained for 6 hours It is c o 01 e d to Q Fifty parts of bonates, either alone or in con3unct1on with anhydrous sodium or potassium acetate formate sodium carbonate, 50 parts of potassium acetate, 15 parts of Cupric acetate and 15 parts of etc., can be used in admixture with any desired copper salt or copper oxide. In forming the cuprous chlor1de are added. The mass is heated to C and maintained for 6 hours. After thiazole ring, the use of these alkaline agents and catalysts is not necessary when working with the cooling, the mass is filtered, the cake washed with nitrobenzene, alcohol and hot water in turn, and 5 alka'h metal salt of the ortho'mercaptoammo' dried. It is obtained in good yields and has the anthra'qumone' We claim: followmg formula" 1. The compounds of the general formula:

in? which it stands for; an element of the group 5. The compound of the formul'az' consistinghf O and S,,y stands for an element of the group consisting of H, C1 and Br, and R- 000I stands for a radical of the group consisting of -OH, -C1, O-a1ky1, -NH2, --NH-a1ky1 and 5; N -NI-I-ary1 in which the O-alkyl group carries from 1 to 18 carbon atoms, the --NH-a1ky1 group from: 1. tor4 carbon atomsand the aryl group is a hydrocarbon radical of the benzene and naphthalene series. 6. The compound of the formula:

2. The compound of the formula:

0 o o -N=N -o 0 OH COOR I N HERMAN E. SCHROEDER. JOSEPH DEINET.

-C0C1 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES- PATENTS Number Name Date 2,175,803 Honold et a1. Oct; 10, 1939 4. The compound of the. formula:

Certificate of Correction Patent No. 2,559,668 July 10, 1951 HERMAN E. SCHROEDER ET AL.

It is hereby certified that error appeare in the printed specification of the above numbered patent requiring correction as follows:

Column 1, lines 49 to 54, right-hand portion of the formula, for

con i read con column 5, lines 3 to 7 right-handportion of the formula, for

" C O 01 C 0 01 read column 7, lines 13 to 16, right-hand portion of the formula, for

coon coon read and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Ollice. Signed and sealed this 25th day of September, A. D. 1951.

THOMAS F. MURPHY,

Assistant Oommz'saioner of Pam.

Certificate of Correction Patent No. 2,559,668 July 10, 1951 HERMAN E. SCHROEDER ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, lines 49 to 54, right-hand portion of the formula, for

COR read column 5, lines 3 to 7, right-hand portion of the formula, for

read

column 7, lines 13 to 16, right-hand portion of the formula, for

C003 COOK read and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Ofiice. Signed and sealed this 25th day of September, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Paton. 

1. THE COMPOUNDS OF THE GENERAL FORMULA: 